EP1249342B1 - Flachdruckplattenvorläufer - Google Patents

Flachdruckplattenvorläufer Download PDF

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Publication number
EP1249342B1
EP1249342B1 EP02007365A EP02007365A EP1249342B1 EP 1249342 B1 EP1249342 B1 EP 1249342B1 EP 02007365 A EP02007365 A EP 02007365A EP 02007365 A EP02007365 A EP 02007365A EP 1249342 B1 EP1249342 B1 EP 1249342B1
Authority
EP
European Patent Office
Prior art keywords
printing plate
cross
hydrophilic
planographic printing
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02007365A
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English (en)
French (fr)
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EP1249342A2 (de
EP1249342A3 (de
Inventor
Miki Takahashi
Koichi Kawamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001110495A external-priority patent/JP3993988B2/ja
Priority claimed from JP2001143893A external-priority patent/JP2002337470A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP1249342A2 publication Critical patent/EP1249342A2/de
Publication of EP1249342A3 publication Critical patent/EP1249342A3/de
Application granted granted Critical
Publication of EP1249342B1 publication Critical patent/EP1249342B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1025—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the present invention relates to a novel planographic printing plate precursor. More specifically, the present invention relates to a planographic printing plate precursor on which an image can be scan-exposed using a laser and based on digital signals, and which is excellent in sensitivity and blemish-resistant.
  • Planographic printing uses a printing plate which includes a oleophilic region to receive ink and an ink-repellent (i.e., hydrophilic) region to receive moistening water.
  • Photosensitive planographic printing plate precursors (“PS plates") are now generally used for planographic printing.
  • a PS plate which comprises a support made of aluminum, for example, and a photosensitive layer provided on the support has become practical and is widely used.
  • This PS plate is used for printing by: image exposing and developing the PS plate to remove the photosensitive layer at non-image portions, and printing using the hydrophilic property of the support surface and the oleophilic property of the photosensitive layer. Accordingly, the support surface of the PS plate must have a good hydrophilic property to prevent blemishes in non-image portions.
  • an anodized aluminum support is used as a hydrophilic support or a hydrophilic layer for a planographic printing plate; this support is generally silicate treated to further increase the hydrophilic property thereof.
  • the hydrophilic support and hydrophilic layer using this aluminum support are now being intensively studied.
  • a support undercoated with polyvinyl sulfonic acid is disclosed in Japanese Patent Application Laid-Open (JP-A) No. 7-1853, and use of a polymer which has a sulfonic acid group as an undercoat of a photosensitive layer is disclosed in JP-A No. 59-101651.
  • Use of a polyvinyl benzonic acid as an undercoat has also been proposed.
  • a hydrophilic layer which comprises a hydrophilic polymer and a hydrophobic polymer, disclosed in JP-A No. 8-292558; a PET support which has a microporous hydrophilic cross-linked silicate surface, disclosed in EP 0709228; and a hydrophilic layer which contains a hydrophilic polymer and is cured by using hydrolyzed tetraalkylorthosilicate, disclosed in JP-A Nos. 8-272087 and 8-507727.
  • hydrophilic layers provide printing plates that exhibit a hydrophilic property, which is improved over the prior art, and produce unblemished printing matter when printing is initiated.
  • these hydrophilic layers have problems such as the hydrophilic layer peeling off from the support after repeated printing, and the hydrophilic property deteriorating over time. Accordingly, there is a demand for a planographic printing plate precursor, which is able to print many sheets with no blemishes and whose hydrophilic layer does not peel off from the support causing the hydrophilic property of the support surface to deteriorate, under even more severe printing conditions. Further, from the viewpoint of utility, there is a demand for an even more improved hydrophilic property.
  • a printing plate for use in a computer-to-plate system for which recent developments have been remarkable, has been widely studied.
  • a planographic printing plate precursor which can be mounted on a printing machine for printing directly after exposure, i.e., without undergoing development, has been studied and various methods using the same have been proposed.
  • One of these methods is known as an on-machine developing, which is carried out in the following manner.
  • An exposed printing plate precursor is mounted on a cylinder of a printing machine. Moistening water and ink are applied to the printing plate precursor while the cylinder is rotated to remove the non-image portion of the printing plate precursor.
  • the processing is completed during printing.
  • the planographic printing plate must have a photosensitive layer that is soluble in moistening water or an ink solvent, and must be able to be handled in daylight so that it can be developed in a printing machine in a bright room.
  • WO 94/23954 discloses a printing plate which needs no developing.
  • This printing plate includes a support and a cross-linking hydrophilic layer provided on the support.
  • the cross-linking hydrophilic layer has a heat-fusing substance encapsulated in micro-capsules.
  • the micro-capsules break and oleophilic substances are eluted from within, whereby the surface of the hydrophilic layer is made hydrophobic.
  • this printing plate precursor requires no developing, it has a problem in that blemishes increase in the non-image portion after repeated printing.
  • An object of the present invention is to provide a positive- or negative-type planographic printing plate precursor which has an improved blemish-resistance and with which much unblemished printed matter can be printed even under severe printing conditions, by disposing thereon a hydrophilic layer having superior persistence and high hydrophilic property.
  • Another object of the present invention is to provide a planographic printing plate precursor which can be made, after an image is formed thereon, by scan-exposure based on digital signals, and either a simple developing operation using water, or by remaining mounted to a printing machine and print without being specially developed.
  • the present inventors as a result of intensive studies, have found that the conventional problems can be solved by introducing a hydrophilic graft chain into the cross-linking hydrophilic layer and forming a negative- or positive-type image forming layer on the cross-linking hydrophilic layer, and accomplished the present invention.
  • the planographic printing plate precursor of the present invention comprises a support and a cross-linking hydrophilic layer disposed thereon, which cross-linking hydrophilic layer has a cross-linking structure and includes a hydrophilic high molecular polymer compound having a hydrophilic graft chain.
  • the planographic printing plate precursor of the present invention is characterized in that the cross-linking hydrophilic layer is produced by reacting, with a cross-linking agent a hydrophilic high molecular polymer compound having, on the backbone polymer thereof, a group which is able to react with the cross-linking agent.
  • a preferable image forming layer includes a high molecular polymer compound having a functional group whose polarity changes between hydrophilic and hydrophobic due to acid, heat or exposure to radiation, and forms an image by using the change between the hydropholic property and hydrophilic property of the surface thereof.
  • the cross-linking hydrophilic layer preferably further includes a compound which is able to form a hydrophobic area on the surface of the cross-linking hydrophilic layer when exposed to heat or radiation.
  • the cross-linked hydrophilic layer has a cross-linking structure formed by a hydrophilic high molecular polymer compound having, on the backbone thereof, a group which is able to react with a cross-linking agent, which high molecular polymer compound being made to react with a cross-linking agent.
  • the tight cross-linking structure imparts, to the cross-linking hydrophilic layer, an excellent hydrophilic property and good ability to withstand repeated printing.
  • the hydrophilic graft chain is introduced into the hydrophilic high molecular polymer compound, and a hydrophilic functional group exists in a form of graft chain which is able to move freely. Therefore, the moistening water can be supplied and removed speedily.
  • the excellent hydrophilic property may effectively suppress blemishes in the non-image portion.
  • the present invention may comprise an image forming layer (i.e., a recording layer) provided on the cross-linked hydrophilic layer.
  • the image forming layer includes a high molecular polymer compound, which has a polarity exchanging group at a side chain thereof, whose polarity changes from one of hydrophilic and hydrophobic to the other, by exposure to at least one of acid, heat and exposure to radiation (hereinafter, "polarity exchanging group").
  • polarity exchanging group a high molecular polymer compound
  • the image can be scan-exposed with a laser, for example, in a short time.
  • on-machine developing can be achieved by making a plate through a simple developing of a printing plate precursor by using water, or by making a plate by mounting a printing plate precursor on a printing machine for printing without undergoing developing.
  • the polarity exchanging group of the high molecular polymer compound used in the image forming layer includes two types of functional groups: a functional group whose polarity changes from hydrophobic to hydrophilic; and a functional group whose polarity changes from hydrophilic to hydrophobic.
  • the present invention also has an advantage of providing both positive- and negative-type planographic printing plates, in the same layer configuration, by selectively employing the high molecular polymer compound having the polarity exchanging group.
  • the cross-linked hydrophilic layer may include, in a matrix composed of a hydrophilic high molecular polymer compound, a compound, such as a heat-fusing hydrophobic particle, which is able to form a hydrophobic area on the surface of the cross-linked hydrophilic layer.
  • a compound such as a heat-fusing hydrophobic particle
  • the heat-fusing hydrophobic particles fuse and coalesce when exposed to heat or radiation to form a hydrophobic area, whereby an image can be formed by scan-exposure with a laser, or the like, in a short time. Accordingly, the cross-linking hydrophilic layer works as the image forming layer.
  • the non-image portion has a good hydrophilic property because of the tightly cross-linking hydrophilic layer, on-machine developing can be achieved by making a plate through a simple developing of a printing plate precursor by using water, or by making a plate by mounting a printing plate precursor on a printing machine for printing without undergoing developing.
  • planographic printing plate precursor of the present invention will be described in detail.
  • the planographic printing plate precursor of the present invention comprises a support and a cross-linking hydrophilic layer provided on the support.
  • a hydrophilic graft chain and a group, which is able to react with a cross-linking agent, are introduced into the cross-linking hydrophilic layer.
  • the cross-linking hydrophilic layer includes a hydrophilic graft polymer chain.
  • the hydrophilic layer which is formed on the support denotes the hydrophilic layer comprising a hydrophilic graft polymer chain.
  • the hydrophilic graft polymer chain bonds with a backbone high molecular polymer compound.
  • the high molecular polymer compound having the hydrophilic graft polymer chain at a side chain thereof is coated or coated by cross-linking on the support.
  • the cross-linking hydrophilic layer having a hydrophilic graft polymer introduced into a polymer cross-linking film structure is simply referred to as, "a cross-linking hydrophilic layer.”
  • the cross-linking hydrophilic layer of the present invention can be prepared by producing the graft polymer in a conventional method, and then cross-linking the graft polymer. Synthesis of the graft polymer is specifically explained in Ide Fumio, "Gurafuto-jugo to sono Oyo (Graft Polymerization and Application Thereof)" Kobunshi Kankoukai, 1977, Koubunshi Gakkai .ed, "Shin Koubunshi Jikkengaku 2, Koubunshi no Gousei/Hanno (New Polymer Experiments 2, Preparation and Reaction of Polymers)” Kyoritsu Shuppan, 1995.
  • a graft polymer can be synthesized basically by one of the following three methods: 1. polymerizing branch monomers from a backbone polymer; 2. bonding a branch polymer with the backbone polymer; and 3. copolymerizing the backbone polymer and the branch polymer ("macromer method").
  • any of the three methods can be employed to produce a hydrophilic surface of the present invention.
  • the macromer method is particularly preferable from the viewpoint of productivity and control of the film structure.
  • hydrophilic macromer such as acrylic acid, acrylamide, 2-acrylamide-2-methylpropane sulfonic acid and N-vinylacetoamide
  • a hydrophilic macromer such as acrylic acid, acrylamide, 2-acrylamide-2-methylpropane sulfonic acid and N-vinylacetoamide
  • Other hydrophilic monomers, including a nonionic group, such as hydroxyl groups, amide groups, sulfonamide groups, alkoxy groups, or cyano groups, can also be used.
  • 2-hydroxyethyl (meth)acrylates (meth)acrylamides, N-monomethylol (meth)acrylamides, N-dimethylol (meth) acrylamides, N-vinylpyrolidones, N-vinylacetamides, arylamines or halogen hydroacid salts thereof, polyoxyethylene glycol mono (meth)acrylates are also useful.
  • hydrophilic macromers which are particularly useful in the present invention include the following: macromers derived from monomers, such as acrylic acids or methacrylic acids having carboxylic groups; sulfonic acid-based macromers derived from monomers, such as 2-acrylamide-2-methylpropanesulfonic acids, vinylstyrene sulfonic acids, or salts thereof; amide-based macromers, such as acrylamides or methacrylamides; amide-based macromers derived from N-vinylcarboxylic acid amide monomers, such as N-vinylacetamides or N-vinylformamides; macromers derived from monomers having hydroxyl groups, such as hydroxyethyl methacrylates, hydroxyethyl acrylates or glycerol monomethacylates; and macromers derived from monomers having alkoxy groups or ethyleneoxide groups, such as methoxyethyl acrylates, methoxypolyethylene glycol acrylates, or polyethylene glycol
  • a useful molecular weight of these macromers is 400 to 100,000, preferably 1,000 to 50,000 and more preferably 1,500 to 20,000.
  • the molecular weight of less than 400 is not preferable in view of the effects and the molecular weight of more than 100,000 is also not preferable in view of polymerizability with a copolymer monomer which forms a main chain.
  • One method of producing a cross-linking hydrophilic layer into which a hydrophilic graft chain is introduced is, after synthesis of the hydrophilic macromers, copolymerizing the hydrophilic macromer and another monomer having a reactive functional group to synthesize a graft copolymerized polymer. Then, coating the synthesized graft copolymerized polymer and the cross-linking agent, which is able to react with the reactive functional group of the polymer, on the support to cause the reaction and the cross-linking therebetween using heat.
  • the cross-linking hydrophilic layer can be prepared by synthesizing a hydrophilic macromer and a graft polymer having a photocross-linkable group or a polymerizable group, and coating the synthesis on the support, then, irradiating light to cause the reaction and the cross-linking therebetween.
  • planographic printing plate precursor of the present invention can be generally produced by dissolving components of the cross-linking hydrophilic layer in a solvent, and coating the resultant solution on a suitable support, and cross-linking.
  • the solvent examples include, but are not limited to, ethylenedichlorides, cyclohexanones, methylethytlketones, methanols, ethanols, propanols, ethylene glycol monomethylethers, 1-methoxy-2-propanols, 2-methoxyethylacetates, 1-methoxy-2-propylacetates, dimethoxyethanes, methyl lactates, ethyl lactates, N,N-dimethylacetamides, N,N-dimethylformamides, tetramethylureas, N-methylpyrrolidones, dimethylsulfoxides, sulfolanes, ⁇ -butyllactones, toluenes, water and the like. These solvents may be used alone, or two or more types may be used in combination.
  • the concentration of the aforementioned components in a solvent is preferably 1 to 50 % by weight.
  • Various methods can be employed to coat the solution on the support. Examples thereof include bar coater coating, rotation coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.
  • the thickness of the cross-linking hydrophilic layer can be selected in accordance with purposes thereof.
  • a dry amount of the cross-linking hydrophilic layer is 0.5 to 5.0 g/m 2 and preferably 1.0 to 3.0 g/m 2 .
  • An amount of less than 0.5 g/m 2 is not preferable because it becomes difficult to achieve effects of the hydrophilic property, and an amount of more than 5.0 g/m 2 is also not preferable because sensitivity and film strength tend to decrease.
  • surfactants may be added to the cross-linking hydrophilic coating solution.
  • examples of the surfactants include a fluorine-based surfactant described in JP-A No. 62-170950.
  • An amount of the surfactants to be added is preferably 0.01 to 1 % by weight and more preferably 0.05 to 0.5 % by weight based on the total solid content of the cross-linking hydrophilic layer.
  • a preferable embodiment of the planographic printing plate of the present invention comprises a support, a cross-linking hydrophilic layer and an image forming layer (i.e., a recording layer which is photosensitive or heat-sensitive) which are disposed on the support in that order.
  • a hydrophilic graft chain and a group that is able to react with a cross-linking agent are introduced into the cross-linked hydrophilic layer.
  • disposed in that order means that the specified layers are disposed on the support in the specified order, but does not exclude other layers, such as an overcoat layer, a primer layer, an intermediate layer, and a backcoat layer, for example, from being provided, so long as the other layers do not inhibit the effects of the present invention.
  • An image forming layer having a high molecular polymer compound that includes a functional group the polarity of which changes from one of hydrophilic and hydrophobic to the other due to acid, heat, or exposure to radiation is preferably used in the present invention.
  • a conventional PS-plate and a positive- or negative-type photosensitive image forming layer, which is known in the art of photo-resisting may also be used.
  • the high molecular polymer compound is a main component of the image forming layer, which is preferable in the present invention.
  • the polarity exchanging group which is to be introduced into the high molecular polymer compound used in the image forming layer, includes two types of functional groups: a functional group whose polarity changes from hydrophobic to hydrophilic; and a functional group whose polarity changes from hydrophilic to hydrophobic.
  • examples of polymers having a polarity exchanging group at a side chain thereof include sulfonic acid ester polymers and sulfonamides described in JP-A No. 10-282672, and carbonic acid ester polymers described in EP 0652483, JP-A Nos. 6-502260 and 7-186562.
  • secondary sulfonic acid ester polymer tertiary carbonic acid ester polymer and carbonic acid alkoxy alkyl ester polymer are particularly preferable.
  • Examples of the sulfonic acid ester polymer and carbonic acid ester polymer are represented by, but are not limited to, the following formulae.
  • Compounds (1p-1) to (1p-8) are sulfonic acid ester polymers, and compounds (a1) to (a10) are carbonic acid ester polymers.
  • the amount thereof is 5 to 99 % by weight, preferably 10 to 98 % by weight, and more preferably 30 to 90 % by weight, based on the total solid content of the image forming layer.
  • polymers which have a functional group at the side chain thereof and whose polarity changes from hydrophilic to hydrophobic, include polymers having ammonium salt groups, described in JP-A No. 6-317899, and polymers, which have decarboxylated polarity exchanging groups, such as sulfonyl acetic acids, represented by the following general formula (1): (wherein x represents -O-, -S-, -Se-, -NR 3 -, -CO-, -SO-, -SO 2 -, -PO-, -SiR 3 R 4 -, and -CS-; R 1 , R 2 , R 3 and R 4 each represents a monatomic group; and M represents an ion which is positively charged.)
  • R 1 , R 2 , R 3 and R 4 examples include -F, -Cl, -Br, -I, -CN, -R 5 , -OR 5 , -OCOR 5 , -OCOOR 5 , -OCONR 5 R 6 , -OSO 2 R 5 , -COR 5 , -COOR 5 , -CONR 5 R 6 , -NR 5 R 6 , -NR 5 R 6 , -NR 5 -COR 6 , -NR 5 -COOR 6 , -NR 5- CONR 6 R 7 , -SR 5 , -SOR 5 , -SO 2 R 5 , and -SO 3 R 5 .
  • R 5 , R 6 and R 7 include hydrogen, alkyl groups, aryl groups, alkenyl groups and alkinyl groups. Examples of these functional groups include the functional groups listed above.
  • hydrogen, alkyl groups, aryl groups, alkenyl groups and alkinyl groups are preferably used as R 1 , R 2 , R 3 and R 4 .
  • the polarity exchanging high molecular polymer compound of the present invention may be a polymer having a hydrophilic functional group listed above, or may be a copolymer of two or more of these monomers. Alternatively, a copolymer of the monomer having one of the hydrophilic functional groups listed above and other monomers may also be used as long as the effects of the present invention are achieved.
  • Examples of the high molecular polymer compound having a functional group, at the side chain thereof, whose polarity changes from hydrophilic to hydrophobic are represented by, but are not limited to, the following formulae.
  • the amount of the polarity exchanging high molecular polymer compound to be present in the image forming layer of the planographic printing plate of the present invention is preferably 0.01 to 94 % by weight and more preferably 0.05 to 90 % by weight based on the total solid content of the image forming layer.
  • image forming layers having various known image forming mechanisms can be employed instead of the polarity exchanging image forming layer. Components used in these conventional image forming layers will be explained below.
  • the following known positive photosensitive layer compositions (a) and (b) are preferably used:
  • a dye having high absorption in the visible light region may be added to the image forming layer of the planographic printing plate precursor of the present invention as a colorant for the image.
  • dyes examples include Oil Yellow #101, Oil Yellow # 103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Co. Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamin B (CI145170B), Marakite Green (CI42000), Methylene Blue (CI52015), and dyes, which are described in JP-A No. 62-293247.
  • an added amount of the dye is 0.01 to 10 % by weight based on the total solid content of the image forming layer.
  • a nonionic surfactant described in JP-A Nos. 62-251740 and 3-208514, and an amphoteric surfactant described in JP-A Nos. 59-121044 and 4-13149 may be added to the image forming layer of the present invention to improve a stability thereof in treatment for development.
  • nonionic surfactant examples include sorbitan tristearates, sorbitan monopalmitates, sorbitan triolates, monoglyceride stearates, and polyoxyethylene nonylphenylethers.
  • amphoteric surfactant examples include alkyl di(aminoethyl) glycines, alkyl polyaminoethyl glycine hydrochlorides, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betains, and N-tetradecyl-N,N-betain type surfactants (for example, Amorgen K, manufactured by DAIICHI INDUSTRIAL CO., LTD.).
  • the amount of the nonioninc and amphoteric surfactants in the image forming layer is preferably 0.05 to 15 % by weight, and more preferably 0.1 to 5 % by weight of the image forming layer of the planographic printing plate precursor.
  • a plasticizer may be added to the image forming layer of the planographic printing plate precursor of the present invention to impart flexibility to the coated film.
  • the plasticizer include butylphthalyls, polyethylene glycols, toributyl citrates, diethyl phthalates, dibutyl phthalates, dihexyl phthalates, dioctyl phthalates, tricresyl phosphates, triburyl phosphates, trioctyl phosphates, tetrahydrofurfuryl oleates, and oligomers and polymers of acrylic acid or methacrylic acid.
  • additives such as known onium salts, haloalkyl-substituted s-triazines, epoxy compounds, vinylether groups, phenol compounds having a hydroxymethyl group described in Japanese Patent Application No. 7-18120, and phenol compounds having an alkoxymethyl group may also be added to the image forming layer.
  • the image forming layer is generally formed by dissolving the foregoing ordinary components in a solvent and then applying the solution on the cross-linking hydrophilic layer.
  • the solvent include, but are not limited to, ethylenedichlorides, cyclohexanones, methylethytlketones, methanols, ethanols, propanols, ethylene glycol monomethylethers, 1-methoxy-2-propanols, 2-methoxyethylacetates, 1-methoxy-2-propylacetates, dimethoxyethanes, methyl lactates, ethyl lactates, N,N-dimethylacetamides, N,N-dimethylformamides, tetramethylureas, N-methylpyrrolidones, dimethylsulfoxides, sulfolanes, ⁇ -butyllactones, toluenes and water.
  • These solvents may be used alone, or two or more types may be used
  • the dry amount (the solid content) of the coated image forming layer can be selected in accordance with purposes thereof.
  • the coated amount of the image forming layer is 0.1 to 10 g/m 2 and preferably 0.5 to 5 g/m 2 .
  • the sensitivity improves.
  • the coated amount becomes too small, the ability to withstand repeated printing deteriorates.
  • the film performance improves.
  • the applied amount becomes too large, the sensitivity becomes insufficient and the reproducibility of fine lines decreases.
  • a variety of methods can be employed to coat the image forming layer. Examples thereof include bar coater coating, rotation coating , spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating and the like.
  • surfactants may be added to the image forming layer of the planographic printing plate precursor of the present invention.
  • the surfactants include fluorine-based surfactants described in JP-A No. 62-170950.
  • An amount of the surfactants to be added is preferably 0.01 to 1 % by weight and more preferably 0.05 to 0.5 % by weight based on the total solid content of the image forming layer.
  • a preferable embodiment of the present invention comprises, a support, a cross-linking hydrophilic layer on the support, into which cross-linking hydrophilic layer a group that is able to react with the cross-linking agent and a hydrophilic graft chain are introduced, and a compound, such as heat-fusible hydrophobic particles or the like, that is able to form a hydrophobic surface region.
  • the cross-linking hydrophilic layer itself has an image forming function.
  • Examples of the compound, which is added to the cross-linking hydrophilic layer, and has the function of image forming, i.e., compounds which are able to form a hydrophobic area when exposed to heat or radiation, include compounds whose polarity may be changed from hydrophilic to hydrophobic when exposed to heat or radiation, or heat-fusing hydrophobic particles.
  • An example of the compound whose polarity may be changed from hydrophilic to hydrophobic include polymers having a functional group whose polarity changes from hydrophilic to hydrophobic as a result of decarboxylation when heated, described in JP-A No. 2000-122272 (Application No. 10-229783).
  • high molecular polymer compounds which are represented by, but are not limited to, the following formulae are preferable. These compounds may preferably have physical properties in that, when coated, the contact angle of water droplets in the air on the film surface is 20° or less before being heated, and is 65° or more after being heated.
  • heat-fusing hydrophobic particle may include polystyrenes described in EP 816070. Hydrophobic particles encapsulated in micro-capsules described in WO 94/23954 may also be used for the same purpose.
  • the heat-fusing hydrophobic particles which are included in the cross-linking hydrophilic layer as an image forming component, fuse to and coalesce with each other due to heat generated by heating or by irradiation with an infrared laser, to form a hydrophobic area (an ink receiving area: the image portion).
  • the particles are formed by hydrophobic organic compounds.
  • the melting point (fusing point) of the hydrophobic organic compound is preferably 50 to 200 °C from the viewpoint of quick fusing of the particles due to a predetermined amount of heat.
  • the fusing point is preferably 80 °C or more, and more preferably 100 °C or more from the viewpoint of stability over time. As the fusing point become greater, the stability increases. However, it is preferable that the fusing point does not exceed 200 °C from the viewpoint of recording sensitivity and ease of handling.
  • hydrophobic organic compound which forms the heat-fusing hydrophobic particle
  • resins such as polystyrenes, polyvinyl chlorides, polymethyl methacrylates, polyvinylidene chlorides, polyacrylonitriles, polyvinyl carbazoles, and copolymers and mixtures thereof.
  • paraffin waxes, microwaxes, polyolefine waxes such as polyethylene waxes and polypropylene waxes
  • fatty acid waxes such as stearoamides, linolenamides, laurylamides, myristylamides, palmitamides and amide oleates, higher fatty acids such as stearic acids, tridecane acids and palmitic acids are also preferably used.
  • the heat-fusing hydrophobic particles which easily fuse to and coalesce with each other due to heat, may be preferably used in the cross-linked hydrophilic layer in the present invention from the viewpoint of image forming property. Further, the heat-fusing hydrophobic particles whose surfaces are hydrophilic and are easily dispersed in water are particularly preferable from the viewpoint of preventing deterioration of the hydrophilic property.
  • hydrophilic property of the surface of the heat-fusing hydrophobic particle it is preferable that the contact angle (with water droplets in the air) of the film, which is coated only with the heat-fusing hydrophobic particles and is dried at a lower temperature than the solidification temperature, be smaller than the contact angle (droplet in the air) of the film, which is coated only with the heat-fusing hydrophobic particles and is dried at a higher temperature than the solidification temperature.
  • hydrophilic polymers or oligomers such as polyvinyl alcohols and polyethylene glycols, or hydrophilic low molecular compounds may be absorbed on the surface of the heat-fusing hydrophobic particle.
  • the method for making the particle surface hydrophilic is not limited to these, and various known methods may be employed to make the surface hydrophilic.
  • the average particle diameter of the heat-fusing hydrophobic particle is preferably 0.01 to 20 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, and the most preferably 0.1 to 1.0 ⁇ m. When the average particle diameter is over 20 ⁇ m, the resolution may be lowered. When the average particle diameter is less than 0.01 ⁇ m, the stability over time may become worse.
  • the amount of the heat-fusing hydrophobic particle to be added is preferably 30 to 98 % by weight and more preferably 40 to 95 % by weight.
  • a support used in the present invention is a dimensionally-stable plate-like substance. Any material may be used for the support as long as the material has a necessary strength, durability, flexibility, and the like. Namely, paper, paper laminated with plastic (e.g., polyethylenes, polypropylenes, and polystyrenes), metal plates (e.g., aluminum, zinc, and copper), plastic films (e.g., cellulose diacetates, cellulose triacetates, cellulose propionates, cellulose butyrates, cellulose acetates/butyrates, cellulose nitrates, polyethylene terephthalates, polyethylenes, polystyrenes, polypropylenes, polycarbonates, and polyvinyl acetals), and paper or plastic film with the above-described metals laminated or deposited thereon are preferably used.
  • plastic e.g., polyethylenes, polypropylenes, and polystyrenes
  • metal plates e.g.,
  • a polyester film or an aluminum plate is preferably used as a support in the present invention.
  • An aluminum plate is particularly preferable since it has good dimensional-stability and can be provided at a relatively low cost.
  • Examples of preferable aluminum plates may include pure aluminum plates and alloy plates comprising aluminum as the main component and trace qualities of different elements. Furthermore, plastic films on which aluminum is laminated or deposited can also be used. Examples of different elements included in an aluminum alloy include silicon, iron, manganese, copper, magnesium, chrome, zinc, bismuth, nickel, and titanium. An amount of the different elements in the alloy is preferably 10 % by weight or less. In the present invention, pure aluminum is particularly preferable. However, since production of a completely pure aluminum is difficult in terms of refining technology, one containing trace qualities of a different element can be used. The composition of an aluminum plate applied in the present invention as mentioned above is not specifically defined, and a known aluminum plate can be also used. The thickness of an aluminum plate used in the present invention is 0.1 to 0.6 mm, preferably 0.15 to 0.4 mm, and more preferably 0.2 to 0.3 mm.
  • a light-to-heat converting substance which changes light energy to heat energy, be included somewhere in the planographic printing plate precursor.
  • the light-to-heat converting substance may be included in, for example, the image forming layer, the cross-linking hydrophilic layer, the surface layer of the support, or the support.
  • the light-to-heat converting substance may be included in a thin layer, which is provided between the image forming layer and the cross-linking hydrophilic layer, or between the surface layer of the support and the support.
  • any light-to-heat converting substance may be used in the planographic printing plate precursor of the present invention as long as the substance absorbs ultraviolet rays, visible light, infrared rays, white light or the like, and converts this into heat.
  • carbon blacks, carbon graphites, pigments, phthalocyanine-based pigments, iron powders, graphite powders, iron oxide powders, lead oxides, silver oxides, chromium oxides, iron sulfides, chromium sulfides and the like are preferably used.
  • a dye, pigment or metal which effectively absorbs infrared rays having a wavelength of 760 nm to 1,200 nm, is particularly preferable.
  • dyes known dyes commercially available or those disclosed in references (e.g., Yuki Gosei Kagaku Kyokai (Organic Synthetic Chemistry Association) ed. "Senryo Binran (Dye Handbook),” 1970, can be used. Namely, azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methyne dyes, cyanine dyes, and metal thiolate complexes are preferably used. Examples of preferable dyes may include cyanine dyes disclosed in JP-A Nos.
  • 59-216146; pentamethyne thiopyrylium salts disclosed in U.S. Patent No. 4,283,475; and pyrylium compounds disclosed in JP-B Nos. 5-13514 and 5-19702 can be preferably used as well.
  • other preferable dyes include near infrared absorption dyes disclosed in U.S. Patent No. 4,756,993 and represented by formulae (I) and (II).
  • these dyes cyanine dyes, squalilium dyes, pyrylium salts, and nickel thiolate complexes are particularly preferable.
  • Pigments usable in the present invention may include commercially available pigments and those disclosed in Nippon Ganryo Gijutsu Kyokai (Japan Pigment Technology Association) .ed, Color Index (C. I.) Manual, “Saishin Ganryo Binran (Current Pigment Manual),” 1977; “Saishin Ganryo Oyo Gijutsu (Current Pigment Application Technology),” CMC Press, 1986; and “Insatsu Inki Gijutsu (Printing Ink Technology),” CMC Press, 1984.
  • pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer bond pigments.
  • insoluble azo pigments azo lake pigments, condensation azo pigments, chelate azo pigment, phthalocyanine pigments, anthraquinone pigments, perylene and perynone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, colored lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, and carbon blacks can be used. Among these, carbon blacks are preferable.
  • These pigments can be used without surface treatment, or can be used after a surface treatment is applied.
  • surface treatment methods include surface coating with resins or waxes, adhering surfactants, and bonding reactive substances (e.g., a silane coupling agent, an epoxy compound, and polyisocyanate) with the pigment surface.
  • bonding reactive substances e.g., a silane coupling agent, an epoxy compound, and polyisocyanate
  • the particle diameter of the pigment is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 1 ⁇ m, and most preferably 0.1 ⁇ m to 1 ⁇ m.
  • the particle diameter of the pigment is less than 0.01 ⁇ m, the stability of the pigment dispersion in a coating solution containing the light-to-heat converting substance may become worse.
  • the particle diameter of the pigment exceeds 10 ⁇ m, the uniformity of a layer containing the light-to-heat converting substance may be adversely affected.
  • known dispersing methods employed in preparing inks or toners can be used.
  • dispersing machines include ultrasonic dispersing machines, sand mills, attritors, pearl mills, super mills, ball mills, impellers, dispersers, KD mills, colloid mills, dynatrons, triple roll mills, and pressure kneaders. Details thereof are described in “Saishin Ganryo Oyo Gijutsu (Current Pigment Application Technology),” CMC Press, 1986.
  • An added amount of the dye or pigment is 0.01 to 50 % by weight, preferably 0.1 to 10 % by weight, and most preferably 0.5 to 10 % by weight for a dye, 3.1 to 10 % by weight for a pigment, based on the total solid content of the layer containing the light-to-heat converting substance.
  • the amount of the pigment or dye is less than 0.01 % by weight, sensitivity becomes insufficient.
  • the amount of the pigment or dye is more than 50 % by weight, the film strength of the layer containing the light-to-heat converting substance decreases.
  • a solution consisting of 17 g of distilled water into which 4 g of the above-prepared macromonomer, 6 g of sodium methacrylate, and 100 mg of 2,2-azobis[2-(2-imidazoline-2-yl)propane] (trade name: VA061, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved was added dropwise to 5 g of distilled water in a flask for 2 hours at 65°C in an atmosphere of nitrogen.
  • an aluminum plate having a thickness of 0.30 mm was degreased with trichloroethylene washing, its surface was made coarse using an aqueous suspension of 400 mesh pumice power by a nylon brush, rinsed well with water.
  • the aluminum plate was etched by immersion in a 25 % by weight of sodium hydroxide aqueous solution at 45 °C for 9 seconds, the plate was rinsed with water, and further immersed in a 2 % by weight of HNO 3 aqueous solution for 20 seconds and then rinsed with water. At this time, the amount of etching of the coarse surface was about 3 g/m 2 .
  • Example 1 Planographic Printing Plate Precursor Having Positive-type Image Forming Layer
  • a cross-linking hydrophilic layer coating solution 1 having the composition below was coated on the above-described aluminum support such that the dry amount of the coating solution was 2 g/m 2 . Then the coating solution 1 was heated for 1 hour at 140 °C to obtain a cross-linking hydrophilic layer.
  • composition of the cross-linking hydrophilic layer coating solution 1 was as follows.
  • An image forming layer coating solution 1 having the composition below was coated, using a rod bar #15, on the above-described cross-linking hydrophilic layer (1) such that the dry amount of the coating solution was 2.6 g/m 2 . Then, the coating solution was dried for 55 minutes at 80 °C to form a positive-type image forming layer and obtain a planographic printing plate precursor A of Example 1.
  • composition of the image forming layer coating solution 1, which is sulfonic acid ester-based was as follows.
  • the positive-type planographic printing plate precursor A thus obtained was exposed imagewise using a Pearl setter (trade name, manufactured by Presstek, exposing conditions: infrared ray laser of 908 nm; output power: 1.2w; and main scanning speed: 2m/sec).
  • the exposed printed plate was mounted on a printing machine (trade name: Ryobi 3200, manufactured by Ryobi Imagix Co. Limited) without being developed.
  • printing was started by using moistening water (trade name: IF201 (2.5 %) and trade name: IF202 (0.75 %), manufactured by Fuji Photo Film Co., Ltd.) and charcoal (trade name: GEOS-G, manufactured by Dainippon Inc & Chemicals, Inc.) as an ink.
  • planographic printing plate obtained from the printing plate precursor of the present invention had an excellent hydrophilic property and an excellent ability to withstand repeated printing.
  • Example 2 Heat-sensitive Planographic Printing Plate Precursor Having Negative-type Image Forming Layer
  • a negative-type planographic printing plate precursor B was produced in the same manner as in Example 1, except that an image forming layer coating solution 2 having the composition below was used to form a negative-type image forming layer.
  • composition of the image forming layer coating solution 2 which is sulfonyl acetic acid-based, was as follows.
  • the obtained negative-type planographic printing plate precursor B was exposed imagewise under the same conditions as in Example 1.
  • the exposed printed plate was mounted on a printing machine (trade name: Ryobi 3200, manufactured by Ryobi Imagix Co. Limited) without being developed. Then, printing was initiated using moistening water (trade name: IF201 (2.5 %) and trade name: IF202 (0.75 %), manufactured by Fuji Photo Film Co., Ltd.) and charcoal (trade name: GEOS-G, manufactured by Dainippon Inc & Chemicals, Inc.) as an ink.
  • a printed matter of high quality was obtained in the initial stage of printing. Subsequently, printing was continued. Even after 2,000 sheets of printed matter were obtained, printed matter of high quality with no blemishes were obtained.
  • the planographic printing plate obtained from the printing plate precursor of the present invention had an excellent hydrophilic property and an excellent ability to withstand repeated printing.
  • Example 3 Heat-sensitive Planographic Prin ting Pla te Precursor Having Heat-fusing Hydrophobic Particles in Cross -linking
  • a coating solution 3 having the composition below was coated such that the coated amount was 2 g/m 2 .
  • the support was then heated and dried for 30 minutes at 100 °C to obtain a planographic printing plate precursor.
  • composition of the cross-linking hydrophilic layer coating solution was as follows.
  • the obtained planographic printing plate precursor was image exposed at 1,751 dpi with a main scanning speed of 3m/sec using a semiconductor laser having a wavelength of 830 nm and a beam diameter of 25 ⁇ m.
  • the exposed printed plate was mounted on a printing machine (trade name: Heidel KOR-D) without being developed and printing was initiated.
  • a printing machine trade name: Heidel KOR-D
  • remaining portions of the image forming layer in non-image portions were removed and a printed matter of high quality was obtained in the initial stage of printing.
  • printing was continued.
  • the planographic printing plate obtained from the printing plate precursor of the present invention had an excellent hydrophilic property and an excellent ability to withstand repeated printing.
  • the planographic printing plate precursor of the present invention has an excellent hydrophilic property which can be preserved under severe printing conditions, and an excellent ability to withstand repeated printing. Thus, with the planographic printing plate precursor of the present invention, many sheets of high-quality printed matters with no blemishes in non-image portions can be obtained. Further, when used with an image forming layer having a high molecular polymer compound, which includes a polarity exchanging group, the planographic printing plate precursor of the present invention can be used to produce a plate by scan-exposure based on digital signals.

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Claims (16)

  1. Planografie-Druckplattenvorläufer, der einen Träger und eine darauf angeordnete, vernetzende, hydrophile Schicht umfasst, worin die vernetzende hydrophile Schicht eine vernetzende Struktur aufweist und eine hydrophile hochmolekulare Polymerverbindung mit einer hydrophilen Pfropfkette einschliesst, wobei die vernetzende hydrophile Schicht hergestellt wird durch Umsetzen einer hydrophilen hochmolekularen Polymerverbindung, die am Polymergrundgerüst eine Gruppe aufweist, die mit dem Vernetzungsmittel reagieren kann, mit einem Vernetzungsmittel.
  2. Planografie-Druckplatte gemäss Anspruch 1, worin die vernetzende hydrophile Schicht und die bilderzeugende Schicht in dieser Reihenfolge auf den Träger aufgebracht sind.
  3. Planografie-Druckplatte gemäss Anspruch 1, worin die vernetzende hydrophile Schicht eine Verbindung umfasst, die einen hydrophoben Bereich auf der Oberfläche der vernetzenden hydrophilen Schicht bilden kann, wenn sie Wärme oder Strahlung ausgesetzt wird.
  4. Planografie-Druckplatte gemäss Anspruch 2, worin die bilderzeugende Schicht eine hochmolekulare Polymerverbindung umfasst, die an ihrer Seitenkette eine die Polarität wechselnde Gruppe aufweist, deren Polarität von hydrophil zu hydrophob und umgekehrt wechselt, wenn sie wenigstens einem, ausgewählt aus Säure, Wärme und Strahlung, ausgesetzt wird.
  5. Planografie-Druckplatte gemäss Anspruch 4, worin die hochmolekulare Polymerverbindung an einer ihrer Seitenketten eine funktionelle Gruppe aufweist, deren Polarität von hydrophob zu hydrophil wechselt.
  6. Planografie-Druckplatte gemäss Anspruch 5, worin die hochmolekulare Polymerverbindung ausgewählt ist aus sekundären Sulfonsäureesterpolymeren, tertiären Kohlensäureesterpolymeren und Kohlensäurealkoxyalkylesterpolymeren.
  7. Planografie-Druckplatte gemäss Anspruch 4, worin die hochmolekulare Polymerverbindung an einer ihrer Seitenketten eine funktionelle Gruppe aufweist, deren Polarität von hydrophil zu hydrophob wechselt.
  8. Planografie-Druckplatte gemäss Anspruch 7, worin die hochmolekulare Polymerverbindung eine decarboxylierende, die Polarität wechselnde Gruppe der folgenden allgemeinen Formel (1) aufweist:
    Figure imgb0036
     worin X -O-, -S-, -Se-, -NR3-, -CO-, -SO-, -SO2-, -PO-, -SiR3R4- und -CS- darstellt; R1, R2, R3 und R4 jeweils eine einwertige Gruppe darstellen und M ein positiv geladenes Ion darstellt.
  9. Planografie-Druckplatte gemäss Anspruch 3, worin sich die physikalischen Eigenschaften der Verbindung, die einen hydrophoben Bereich auf der Oberfläche der vernetzenden hydrophilen Schicht bilden kann, von hydrophil zu hydrophob ändern, wenn sie Wärme oder Strahlung ausgesetzt wird.
  10. Planografie-Druckplatte gemäss Anspruch 9, worin die Verbindung ausgewählt ist aus Verbindungen der folgenden Formeln:
    Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
  11. Planografie-Druckplatte gemäss Anspruch 3, worin die Verbindung, die einen hydrophoben Bereich auf der Oberfläche der vernetzenden hydrophilen Schicht bilden kann, wenn sie Hitze oder Strahlung ausgesetzt wird, durch eine hydrophobe organische Verbindung gebildet wird und warmschmelzende hydrophobe Teilchen umfasst, die aufgrund der durch Bestrahlung mit einem Infrarotlaser erzeugten Wärme verschmelzen und ineinanderlaufen und einen hydrophoben Bereich bilden.
  12. Planografie-Druckplatte gemäss Anspruch 11, worin der Schmelzpunkt der hydrophoben organischen Verbindung, die die warmschmelzenden hydrophoben Teilchen bildet, 50 bis 200°C beträgt.
  13. Planografie-Druckplatte gemäss Anspruch 11, worin die hydrophobe organische Verbindung, die die warmschmelzenden hydrophoben Teilchen bildet, ausgewählt ist aus Polystyrolen, Polyvinylchloriden, Polymethylmethacrylaten, Polyvinylidenchloriden, Polyacrylnitrilen, Polyvinylcarbazolen, Copolymeren und Mischungen daraus, Polyolefinwachsen, Fettsäurewachsen und höheren Fettsäuren.
  14. Planografie-Druckplatte gemäss Anspruch 11, worin der durchschnittliche Teilchendurchmesser der warmschmelzenden hydrophoben Teilchen 0,01 bis 20 µm beträgt.
  15. Planografie-Druckplatte gemäss Anspruch 11, worin die Zugabemenge der warmschmelzenden hydrophoben Teilchen 30 bis 98 Gew.% beträgt, bezogen auf den Gesamtfeststoffgehalt der vernetzenden hydrophilen Schicht.
  16. Planografie-Druckplatte gemäss Anspruch 1, worin die Trockenmenge der vernetzenden hydrophilen Schicht 0,5 bis 5,0 g/m2 beträgt.
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